期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 107, 期 8, 页码 3367-3372出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0914693107
关键词
photochemistry; proton-coupled electron transfer; water as proton acceptor
资金
- Agence Nationale de la Recherche
Three experimental techniques, laser flash photolysis, redox catalysis, and stopped-flow, were used to investigate the variation of the oxidation rate constant of phenol in neat water with the driving force offered by a series of electron acceptors. Taking into account a result previously obtained with a low-driving force electron acceptor thus allowed scanning more than half an electron-volt driving force range. Variation of the rate constant with pH showed the transition between a direct phenol oxidation reaction at low pH, where the rate constant does not vary with pH, and a stepwise reaction involving the prior deprotonation of phenol by OH-, characterized by a unity-slope variation. Analyses of the direct oxidation kinetics, based on its variation with the driving force and on the determination of H/D isotope effects, ruled out a stepwise mechanism in which electron transfer is followed by the deprotonation of the initial cation radical at the benefit of a pathway in which proton and electron are transferred concertedly. Derivation of the characteristics of counterdiffusion in termolecular reactions allowed showing that the concerted process is under activation control. It is characterized by a remarkably small reorganization energy, in line with the electrochemical counterpart of the reaction, underpinning the very peculiar behavior of water as proton acceptor when it is used as the solvent.
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